Water-repelling composition



Patented F eb. 16, 1954 WATER-REPELLING COMPOSITIQN Racine, Wis., as'signor to Norman G. Mailander,

S- C, Johnson. 6:. So

11, Inc., Racine, Wis.

No Drawing. Application September 8, 1950,

Serial No. 183,916

3 Qlaims. 1

This invention relates to the treatment of fabrics to render them water-repellent. More particularly, the invention relates to solutions of certain waxy materials and a novel water re.- pelling agent, substantive to fabrics and capable of imparting water-repellent eifects to them.

Materials and methods advocated by prior art to impart water-repellency to fabrics have been sundry and numerous. Whereas a comparatively high degree of resistance has been effected upon wool with compositions of both the aqueous dispersion and non-aqueous solution varieties, such has not been accomplished without a subsequent curing operation with other extensively used fabrics, especially cotton. It has been found that cotton may be transmitted a satisfactory degree of repellency when treated with certain aqueous dispersions or with what is known in the trade as a laundry type composition. However, no material or composition has been disclosed which has proved satisfactorily operable upon cotton material when such is dry cleaned. Nevertheless, the latter method of cleaning cotton garments which require watcr-repelleney (raincoats, jackets, etc.) is preferred, since the laundering of such garments causes shrinkage, color fading and subsequent diiiicult ironing or pressing.

It is therefore the object of this invention to provide a composition which will oiier not only an optimum degree of water-repellency to wool, but will permit the dry cleaning of such fabrics as cotton and result in a heretofore unattained repellency of the fabric without the necessity of subsequent curing.

This novel composition is a solution comprising from 1 to 10% by Weight of the material selected from. the, group consisting of petroleum waxes, petrolatums, polymerized octadecyl vinyl ether and mixtures thereof, zirconium ethoxide and a mutual solvent for said material and said zirconium ethoxide. The solvent constitutes the major portion by weight of said solution.

In my c p s ppl cation, S. N. 183 .9l water-repelling compositions are formed with alkoxides havin from 3 to 18 carbon atoms- Now, having indicated in a general Way, the nature and purpose of this invention, the fol, lowing examples will illustrate the invention. It is understood, however, that such examples are presented merely as illustrations of the inven-- tion, and are not to be construed as limiting the same. In the examples, the ingredients are given in parts by weight, unless otherwise indicated.

Exampl 1 Forty parts of refined parafiin wax was dissolved in 893 parts of toluene by heating the mixture in a suitable vessel to a temperature of approximately F. In a second vessel, 1 part of zirconium ethoxide was dissolved in 166 parts of toluene by heating to a temperature of approximately 230" F. while the mixture was simultaneously agitated. At this stage, the solution appeared clear and was combined with the ingredients of the first vessel and allowed to cool to approximately room temperature. A swatch of wool gabardine and a swatch of cotton twill material were dipped in the cooled solution and remained immersed therein for a period of two minutes after which they were withdrawn from the solution bath and the liquid constituents of thecornposition withdrawn from the swatches by means of centrifuging. The swatches were then exposed to the atmosphere for a period of five to six hours and upon drying were steam pressed in a manner simulating commercial pressing methods. The swatches were then submitted to a spray test to determine the degree of -water-repellency. The test apparatus consisted of a 65inch glass laboratory funnel held by a laboratory ring support. A spray nozzle connected to the funnel tube by a piece of %-inch rubber tubing, was provided with as holes, drill number 65, 0.035 inch in diameter. The nozzle was supported directly over the center of an embroidery hoop mounted on a block of wood, so that the plane of the swatch held on the hoop made an angle of 45 with the horizontal. The distance of the nozzle to the center of the hue mounted swatch was 6 inches.

250 ml. of water having a temperature of 80i1 was, quickly poured into. the funnel and allowed to spray down upon the fabric. The dwration of the. spraying approximately 25 to 30 seconds. Upon completion of the spraying period, the hoop was grasped at one edge and the other edge tapped against a solid object, the fabric facing this object during tapping. The hoop was then turned 180, grasped at the 011+ posite end and tapped at the, point previously held. The swatch was then examined and dos ienated a spray rating The cotton twill indicated a ratmg of 80 and the. wool gabardine swatch indicated a. rating of 108.

Example 2 Forty parts of refined paraflin wax was melted by heating to a temperature of approximate y F. and in this melted condition were added to 59 parts of toluene.

One part of zirconium ethoxide was then mixed with the wax solution and dissolved therein. A portion of the composition was then placed in a charge cup of a siphon type pressure spray from which the solution was prayed upon two swatches, one of wool and the other of cotton, with a gun pressure of approximately lbs. p. s. i. The spray was moved over the swatches at a rate sufiicient to allow visual notice of wetting caused by the delivery of the composition upon the fabric. The swatches were then dried and pressed in a manner similar to that used in commercial pressing establishments and thereupon submitted to spray rating tests identical to those disclosed in Example 1 and it was indicated that the cotton possessed a spray rating of 90 and the wool swatches had a rating of 100.

Example 3 found that as a result of both the spray and dip method, the fabric, cotton and wool alike, possessed a spray rating of 100. Y

Example 4 Av solution was prepared with parts of zirconium ethoxide, 5 parts refined parafhn wax and 905 parts of solvent. Cotton swatches were then sprayed with material as described in Example 2 and additional swatches were clipped and treated as described in Example 1. The

spray rating tests were conducted and the cotton fabric was found to have a spray rating of 50.

Example 5 A solution was prepared containing 3 parts of zirconium ethoxide, parts of polymerized octadecyl vinyl ether and 957 parts of solvent. A number of wool gabardine and cotton swatches were dipped in the material while others were sprayed with 2. A 100 spray wool and the cotton fabric.

Example 6 A solution was prepared with 100 parts of refined paraflin wax, 16.5 parts of zirconiumethoxide and 883.5 parts of solvent. The composition was then placed in an aerosol bomb wherein it constituted by weight of the contents of the bomb; the remaining 40% consisting of the propellent, dichlorodifluoromethane. Wool and cotton swatches were sprayed with the solution delivered from the aerosol bomb, and both types of material indicated a spray rating of 100.

In order to determine the spray :rating of the swatches in theexamples, after the procedure described in Example 1, the fabric is examined and compared to a series of photographs of water-contacted fabric which constitute a standard chart for rating the fabrics tested. The following ratings indicate the following conditions:

0-complete wetting .of whole of upper and lower surfaces. 50- complete wetting of whole of upper surface. IO-partial wetting of whole of upper surface.

'eral Specifications, Test Methods,

25693524 7 f' 1 I t.

H4 -wetting of upper surface at spray points. -slight random sticking or wetting of upper surface.

-no sticking or wetting of upper surface.

This test is described in a Federal Standard Stock Catalog, in section IV (part 5) of a supplement to Federal Specification for Textiles; Gendated October In the examples, as little as .1 per cent (Examples 1 and 2) to as much as 3 per cent (Example 3) of zirconium ethoxide was incorporated.

the solution described in .Example P rating was evidenced by both the dences itself upon not sufiiciently soluble therein.

Where more than 3 per cent of the water-repelling agent is employed, incidental spotting evithe fabric treated. Not less than .1 per cent of the water-repelling agent should be used, for if less than that amount be incorporated into the composition, a degree of water-repellency will be rendered which is not greatly improved over that of compositions teach- 'ing, the application of waxy materials without the .addition of the water-repelling agent.

Not less than one per cent nor more than 10 per cent of petroleum wax, petrolatum, or polymerized octadecyl vinyl ether should be included in the solution. Where more than 10 per cent by weight of the composition is one of these materials, the film formed by the solution upon the fabric gives the fabric an undesirable stiffening efiect. Where less than one per cent by weight of the waxy material is contained in the solution, as shown in Example 4, the degree of waterrepellency imparted to the fabric is substantially lowered and practically of no improvement over heretofore disclosed repelling compositions.

It should be appreciated that no vegetable or animal waxes may be utilized, and only the specific waxy materials as set forth above, since it is only these materials which are completely soluble at room temperature which ofier a substantial increase in water-repellency when combined with the water-repelling agent. It is mandatory that the waxy material be completely in solution at room temperature and that no throw out occur (as would be the case with vegetable and animal waxes), since if such were the condition, the minute solidified particles of the. waxy material would evidence themselves upon the fabric treated. However, treating fabric with a solution in which any of the specified materials is included as the waxy constituent, no visual trace of the material is observed upon the fabric.

Whereas certain solvents are disclosed in the examples, any volatile liquid, aromatic hydrocarbon or halogenated hydrocarbon is operable. The aromatic hydrocarbons include benzene, toluene, etc. Aliphatic hydrocarbons, i. e., the naphthas, may not be used since the ethoxide is Examples of operable halogenated hydrocarbons are carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. It should be appreciated that the operable solvents are critically limited to but these two classes since it has been found that solvents of other classes are either incapable of placing the waxy material or the zirconium ethoxide in solution or are deficient in that products employing them as a vehicle often render the treated fabric an undesirable spotting effect. The selected solvent constitutes the major portion by weight of the solution.

Where the ethoxide is employed in a quantity close to the upper limit of the proposed range, and the water-repellent solution is applied to the fabric by dipping it therein, if a suflicient amount of moisture remains in the fabric, spotting of the water-repellent film may occur thereupon. To overcome such a condition, it is advocated that a reactive agent such as octylene glycol be incorporated in the water-repellent solution since this material appears to react with the ethoxide to cause an alcohol exchange, thereby eliminating spotting and causing the zirconium compound to be less reactive with water, i. e., rendering it more stable and less susceptible to decomposition.

It has been found that certain resins, such as acrylic resins, pentaerythritol ester of abietic acid, butadiene styrene copolymers, terpene resins, etc., may be incorporated in the solution and, with fabrics of certain texture, aid in the impartment of water-repellency, but in no case may such resins be substituted in lieu of the waxy material.

As illustrated in the examples, methods of applying the solution are not critical, i. e., it has been illustrated that dip, spray and aerosol methods are highly operable and functional.

Obviously, the compositions of the invention are not limited to those which contain any par ticular number of components but must contain the novel water-repellent agent, zirconium ethoxide, and one or more of the specified Waxy constituents within the limited ranges.

I claim:

1. A solution for rendering fabric water-repellent, consisting essentially of from 1 to 10% by weight of a material selected from the group consisting of petroleum waxes and polymerized octadecyl vinyl ether, from .1 to 3% of zirconium ethoxide and a solvent selected from the group consisting of volatile aromatic liquid hydrocarbons and liquid aliphatic halogenated hydrocarbons, said solvent constituting the major portion by weight of said solution.

2. A solution for rendering fabric water-repellent, consisting essentially of from 1 to 10% by weight of petroleum waxes, from .1% to 3% of zirconium ethoxide and a solvent selected from the group consisting of volatile aromatic liquid hydrocarbons and liquid aliphatic halogenated hydrocarbons, said solvent constituting the major portion by weight of said solution.

3. A solution for rendering fabric Water-repellent, consisting essentially of from 1 to 10% by weight of polymerized octadecyl vinyl ether, from .1% to 3% of zirconium ethoxide and a solvent selected from the group consisting of volatile aromatic liquid hydrocarbons and liquid aliphatic halogenated hydrocarbons, said solvent constituting the major portion by weight of said solution.

NORMAN G. MAILANDER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,456,283 Jefferson Dec. 14, 1948 FOREIGN PATENTS Number Country Date 604,002 Great Britain Sept. 23, 1948 120,451 Sweden Dec. 16, 1947 OTHER REFERENCES The Chemistry and Technology of Waxes, by Warth; published, 1947, by Reinhold Pub. Corp, New York, N. Y.

Textile Finishing, Marsch; Chapman and Hall Ltd., London, 1948; page 470. 

1. A SOLUTION FOR RENDERING FABRIC WATER-REPELLENT, CONSISTING, ESSENTIALLY OF FROM 1 TO 10% BY WEIGHT OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF PETROLEUM WAXES AND POLYMERIZED OCTADECYL VINYL ETHER, FROM 91 TO 3% OF ZIRCONIUM ETHOXIDE AND A SOLVENT SELECTED FROM THE GROUP CONSISTING OF VOLATILE AROMATIC LIQUID HYDROCARBONS AND LIQUID ALIPHATIC HALOGENATED HYDROCARBONS, SAID SOLVENT CONSTITUTING THE MAJOR PORTION BY WEIGHT OF SAID SOLUTION. 